TECHNICAL REPORT RAPPORT TECHNIQUE TECHNISCHER BERICHT CEN/TR 196-4 September 2007 ICS 91.100.30 Supersedes ENV 196-4:1993 English Version Methods of testing cement - Part 4: Quantitative determination of constituents Méthodes d'essais des ciments - Partie 4 : Détermination quantitative des constituants Prüfverfahren für Zement - Teil 4: Quantitative Bestimmung der Bestandteile This Technical Report was approved by CEN on 14 April 2007. It has been drawn up by the Technical Committee CEN/TC 51. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels 2007 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TR 196-4:2007: E
Contents Page Foreword... 3 1 Scope... 5 2 Normative references... 6 3 General requirements for testing... 7 3.1 Number of tests... 7 3.2 Determination of constant mass... 7 3.3 Expression of masses and results... 8 3.4 Repeatability and reproducibility... 8 4 Preparation of a cement sample... 8 5 Reagents... 8 6 Determination of the contents of cement constituents... 8 6.1 General... 8 6.2 Selective dissolution method... 9 7 Determination of the contents of constituents for cements with three constituents16 7.1 General... 16 7.2 Determination of the slag content... 16 7.3 Determination of the siliceous fly ash content... 26 7.4 Determination of the natural pozzolana content... 28 2
Foreword This document (CEN/TR 196-4:2007) has been prepared by Technical Committee CEN/TC 51 Cement and building limes, the secretariat of which is held by NBN. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights. This document supersedes ENV 196-4:1993. This European Technical Report was drawn up by Technical Committee CEN/TC 51 "Cement and building limes" the Secretariat of which is held by NBN. It is based on a revision of the European Prestandard ENV 196-4 of July 1993. The main aim of this document is to quantitatively verify the compositions (analysis of the constituents) of all the cements included in EN 197-1:2000 (Cements Part1: composition, specifications and conformity criteria for common cements) as set out in Table 1 The 27 products in the family of common cements. Further to this objective, original methods of analysis were devised, firstly, for cements with 3 constituents and then a reference method for cements with more constituents. Following the progress of work on EN 197-1, cements with blastfurnace slag, siliceous fly ash and natural pozzolans have been successively studied. As a result the first draft of ENV 196-4 was published in December 1989, followed by the ENV 196-4 in July 1993. The main aim of the revision of the Pre-standard was to adapt the reference method in such a way that it would be qualitative and quantitative whatever the constituent materials, including blastfurnace slag (which had not been included in the 1989 draft ENV 196-4). This entailed revising the analytical procedure and the calculation of the constituents. The opportunity was taken at the same time to unify the presentation of the different methods, reference and alternative, endeavoring to standardize the notational symbols to eliminate all ambiguities in the interpretation of the formulae for calculations. Table 1 of ENV 197-1:1992 introduced further new constituent materials. One of them, silica fume, could be routinely determined by the reference method, while calcareous fly ash and burnt shale, being composites of several minerals, react partially like other constituents capable of being determined by the reference method. Where these materials are constituents it has proved not to be possible to determine the mass composition of the cement but only to obtain an overall bulk analysis. Almost all of the cements manufactured in Europe can be correctly characterized and quantified by the reference method. However, for cements containing burnt shale (CEM II/A-T and B-T) or calcareous fly ash (CEM II/A-W and B-W) it would be necessary to undertake further research in order to obtain an acceptable reference method. For cements having constituents that can be analyzed by the current reference method as defined in section 1 Scope the method will be adequate. Where other constituents are known, or suspected, to be included it will be necessary to develop additional methods for the quantitative determination of those particular constituents. The European Standard on the methods of testing cement comprises the following Parts: EN 196-1 Methods of testing cement Part 1: Determination of strength 3
EN 196-2 Methods of testing cement Part 2: Chemical analysis of cement EN 196-3 Methods of testing cement Part 3: Determination of setting times and soundness EN 196-5 Methods of testing cement Part 5: Pozzolanicity test for pozzolanic cement EN 196-6 Methods of testing cement Part 6: Determination of fineness EN 196-7 Methods of testing cement Part 7: Methods of taking and preparing samples of cement EN 196-8 Methods of testing cement Part 8: Heat of hydration Solution method EN 196-9 Methods of testing cement Part 9: Heat of hydration Semi-adiabatic method. NOTE A previous Part, EN 196-21: Methods of testing cement Part 21: Determination of the chloride, carbon dioxide and alkali content of cement, has been revised and incorporated into EN 196-2 4
1 Scope This European Technical Report describes procedures for determining the contents of most of the constituents of the cements that fall within the scope of EN 197-1. In principle, the method described in Clause 6 applies to all cements, whatever the number and nature of their constituents, but in practice is limited to the cements identified in Table 1. The method in clause 6 should be considered to be the method of choice and is based on a sequential selective dissolution of the cement s constituents, generally of an unknown number, where they are not available separately for analysis at the same time as the cement. The method of choice enables the quantitative determination (by mass) of: Portland cement clinker, blastfurnace slag, siliceous fly ash, natural pozzolans, limestone, silica fume and set regulators in cements of the types identified in Table 1. Table 1 is derived from Table 1 of EN 197-1. Type of cement Table 1 Common cement types specified in EN 197-1 Designation Notation Excluding (1) CEM I Portland cement I CEM II CEM III Portland-slag cement (with blastfurnace slag) Portland-silica fume cement Portland pozzolana cement (with natural pozzolana) Portland-fly ash cement (with siliceous fly ash) Portland-limestone cement Portland-composite cement Blastfurnace cement II/A-S II/B-S II/A-D II/A-P II/B-P II/A-V II/B-V II/A-L or LL* II/B-L or LL* II/A-M II/B-M III/A III/B III/C CEM IV Pozzolanic cement IV/A IV/B CEM V Composite cement V/A V/B limestone Burnt shale *The method is incapable of distinguishing between limestones of type L and LL NOTE 1 Where cements contain calcareous fly ash, burnt shale and/or constituents that partly contain mineral phases, similar to those of clinker, further investigation into the characteristics of those constituents will be necessary before the method can be applied. 5
The method of choice has limitations, as indicated earlier, and cannot be considered to be a means by which clinker content can simply be determined in isolation from any other constituent. Clinker content is determined by difference and other constituents contain, in part, mineral phases similar to those present in clinker and can cause interferences that lead to difficulties in interpretation of the results. Where apparently anomalous results are obtained, it is recommended that further investigations are undertaken in accordance with the procedure given in Section 6.2.5.4. Any other method with the same objectives, and intended for use where the constituents are unavailable for separate analysis, can be considered to be an alternative to the method of choice when it is shown that, with appropriate statistical validity, it gives equivalent results. In individual cases, where the laboratory has been formally advised that: the cement contains only two constituents, the method is greatly simplified because it is sufficient to determine the set regulator content (R) in order to be able to calculate the clinker content by difference; the cement contains only three constituents, i.e. a set regulator, clinker and one of the following three: slag, pozzolana or siliceous fiy ash. Some of the methods in clause 7 are variations on the method of choice whereas others are based on physical separation of constituents and different analytical principles. NOTE 2 This European Technical Report adopts the following use of terms for major constituents: Portland cement clinker as defined in EN 197-1 is referred to as clinker ; granulated blastfurnace slag as defined in EN 197-1 is referred to as slag ; natural pozzolans as defined in EN 197-1 is referred to as pozzolans ; siliceous fly ash as defined in EN 197-1 is referred to as fly ash ; calcium sulfate as defined in EN 197-1 is referred to as set regulator. 2 Normative references This European Technical Report incorporates by dated or undated reference provisions from other publications. These normative references are cited at the appropriate places in the text and the publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply to this European Technical Report only when incorporated in it by amendment or revision. For undated references the latest edition of the publication referred to applies. EN 196-2, Methods of testing cement Part 2: Chemical analysis of cements EN 196-7, Methods of testing cement Part 7: Methods of taking and preparing samples of cement EN 197-1, Cement Part 1: Composition, specifications and conformity criteria for common cements ISO 3534, Statistics Vocabulary and symbols 6